WO1997037848A1 - Layer material - Google Patents

Layer material Download PDF

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Publication number
WO1997037848A1
WO1997037848A1 PCT/FI1997/000184 FI9700184W WO9737848A1 WO 1997037848 A1 WO1997037848 A1 WO 1997037848A1 FI 9700184 W FI9700184 W FI 9700184W WO 9737848 A1 WO9737848 A1 WO 9737848A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
layers
hydroxyvaleric
hydroxybutyric
basic
Prior art date
Application number
PCT/FI1997/000184
Other languages
French (fr)
Inventor
Hannu Karhuketo
Original Assignee
Upm-Kymmene Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Upm-Kymmene Oy filed Critical Upm-Kymmene Oy
Priority to US08/952,902 priority Critical patent/US6080478A/en
Priority to DE1997622560 priority patent/DE69722560T2/en
Priority to EP97914338A priority patent/EP0842048B1/en
Priority to JP53586797A priority patent/JPH11506990A/en
Publication of WO1997037848A1 publication Critical patent/WO1997037848A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/3179—Next to cellulosic

Definitions

  • the invention relates to a layer material according to the introductory part of the accompanying claim 1.
  • packaging laminates by combining a cellulose-based, naturally decomposing basic layer with layers of biodegradable plastic which improve the tightness of the basic layer. This way total compostability of the material in the waste management of the packaging material can be achieved.
  • a biodegradable laminate used as packaging material is known.
  • This laminate consists of polyhydroxybutyrate-based copolymer, more precisely hydroxybutyric- hydroxyvaleric copolyester (HB/HV) coextruded together with a polyethylene film on a cellulose-based sheet.
  • the polyethylene film is used as an auxiliary film in the coextrusion process, and after the process it is pulled of the laminate leaving the hydroxybutyric/hydroxyvaleric film attached to the sheet.
  • the biodegradable polymer in question has good barrier properties (barrier layer properties) in itself and is therefore a popular laminating agent, and it can be used to increase the tightness of cellulose-based basic materials noticeably.
  • the European application publication 603876 introduces the use of hydroxybutyric/hydroxyvaleric copolymer layers as water vapour barrier on both sides of an oxygen barrier layer of polyvinyl alcohol.
  • the layers are laminated either on one side or both with a layer of cellulosic derivative or paper.
  • the purpose of this invention is to provide a layer material which exhibits improvements to the aforementioned properties and which can be used as airtight and biodegradable packaging materials.
  • the layer material is primarily characterized in what is presented in the characteristic part of the accompanying claim 1.
  • the invention combines the excellent properties of polyhydroxyalcanoate and polylactide.
  • polyhydroxyalcanoate layers such as polyhydroxybutyric- based layers, particularly hydroxybutyiic-hydroxyvaleric copolymer layers
  • good barrier properties can be achieved with layers of great thinness, even of only micrometers thick, when they are combined with polylactic acid, i.e. polylactide (PLA) which improves the processability of the material.
  • PLA polylactide
  • Polylactide exhibits good adhesion properties and it does not stick to the surface of the chill roll in coextrusion which means that also the coextrusion chances of the hydroxybutyric/ hydroxyvaleric copolymers are improved, among other things edge weaving is reduced and the nucleant can be omitted.
  • Figure 1 shows a schematic view of the layer material according to the invention
  • Figure 2 shows the process for manufacturing the material.
  • Figure 1 includes a cellulose-based and naturally decomposing basic layer 1, which gives the product its strength, the basis weight of which may vary within the known values for paper and cardboard.
  • a polylactide layer 1 (PLA) which attaches the other plastic layers to the basic layer by adhesion, a hydroxybutyric/hydroxyvaleric copolymer layer 3 (HB/HV), a polylactide layer 4, a hydroxybutyric/hydroxyvaleric copolymer layer 5 and a polylactide layer 6 which forms the outer layer.
  • PLA polylactide layer 1
  • HBV hydroxybutyric/hydroxyvaleric copolymer layer 3
  • a polylactide layer 4 a hydroxybutyric/hydroxyvaleric copolymer layer 5
  • a polylactide layer 6 which forms the outer layer.
  • all the plastic layers are biodegradable which in this case denotes that their polymer structures are naturally such that the polymer chains degrade under compost conditions.
  • the layer material can be used as a packaging material for purposes when the escape of water vapour, oxygen or aroma is wished to be prevented, particularly for the packaging of food stuffs, cosmetics and industrial chemicals.
  • the polylactide layer 4 in the middle also attaches the HB/HV layers 3 and 5, which act as barrier layers, to each other.
  • the HB/HV layers 3 and 5 can be formed very thin, and their barrier properties as separate layers are better than those of a uniform layer of the same total thickness. Due to the aforesaid properties, the HB/HV qualities may be more freely selected.
  • the heat-sealing properties of the outermost PLA layer may be utilized in forming food stuff packaging containers or in attaching additional layers to the material.
  • a further good property of polylactide is its inexpensiveness.
  • PLA polylactide
  • HB/HV copolymer HB/HV copolymer
  • the plastic layers are usually in contact with the packaged product. It is also possible to further add the same layers to the layer material in Fig. 1 so that they succeed one another by turns as described.
  • the outermost PLA layer 6 can be omitted, in which case the layer 5 forms the outer layer. This is suitable for liquid packaging containers because of the good water resistance of HB/HV or its equivalent. If the outer layer is PLA it is suitable to the packaging of greasy food stuffs.
  • polyhydroxyalcanoate may also be used, preferably polyhydroxybutyrate (PHB) or its copolymer with another hydroxyalcanoate, such as the aforementioned HB/HV.
  • PHB polyhydroxybutyrate
  • the hydroxybutyric/hydroxyvaleric copolymer may be, for example, one with 92
  • hydroxybutyric units % of hydroxybutyric units and 8 % of hydroxyvaleric units, which is sold under the trade name "BIOPOL” by the Zeneca Ltd.
  • the number of hydroxyvaleric units in the copolymer may vary, and it may be within, for example, the range 1 - 20 p-
  • the basic layer 1 may be paper used in food stuff packaging containers, cardboard or preferably greaseproof paper which has good grease and aroma tightness, for example 100 - 600 s as Linden tightness.
  • the basis weight of the basic layer may vary considerably, for example in the range 30 - 500 g m 2 .
  • FIG. 2 shows the principle for manufacturing the layer material.
  • the coextruder 7 comprises a feed block 8 into which the aforesaid two biodegradable polymer materials are fed (marked with letters HB/HV and PLA).
  • the feed block arranges the materials into five layers one on top of each other, after which the forming die 9 spreads them into a film of full-width which is lead into the nip between the press roll 10 and the control roll 11 , into which nip the material forming the basic layer 1 is brought from its own roll.
  • the finished layer material is lead along the surface of the control roll 11 to further processing
  • a possibility to add an additional layer on top of the plastic layer comprised of layers 2 - 6 is marked with a dotted line, the additional layer being preferably also a cellulose- based naturally decomposing material.
  • the additional layer being preferably also a cellulose- based naturally decomposing material.

Abstract

The layer material comprises a cellulose-based naturally decomposing basic layer (1) and on top of it layers (3, 5) of polyhydroxyalcanoate, such as hydroxybutyric/hydroxyvaleric copolymer (HB/HV). To produce good adhesion, surface and barrier properties to the product used as a packaging material, there is a layer (4, 2) of biodegradable polylactide (PLA) between the aforesaid layers (3, 5) and between these layers and the basic layer (1).

Description

LAYER MATERIAL
The invention relates to a layer material according to the introductory part of the accompanying claim 1.
It is known to make packaging laminates by combining a cellulose-based, naturally decomposing basic layer with layers of biodegradable plastic which improve the tightness of the basic layer. This way total compostability of the material in the waste management of the packaging material can be achieved.
From the European application publication 534471 , for example, a biodegradable laminate used as packaging material is known. This laminate consists of polyhydroxybutyrate-based copolymer, more precisely hydroxybutyric- hydroxyvaleric copolyester (HB/HV) coextruded together with a polyethylene film on a cellulose-based sheet. The polyethylene film is used as an auxiliary film in the coextrusion process, and after the process it is pulled of the laminate leaving the hydroxybutyric/hydroxyvaleric film attached to the sheet.
The biodegradable polymer in question has good barrier properties (barrier layer properties) in itself and is therefore a popular laminating agent, and it can be used to increase the tightness of cellulose-based basic materials noticeably.
In addition, the European application publication 603876 introduces the use of hydroxybutyric/hydroxyvaleric copolymer layers as water vapour barrier on both sides of an oxygen barrier layer of polyvinyl alcohol. The layers are laminated either on one side or both with a layer of cellulosic derivative or paper.
The multi layer structure in question does not provide satisfactory properties. Polyvinyl alcohol tends to dissolve in water which makes it difficult to be used under conditions of considerable humidity. Furthermore, the coextrusion of these materials is in practise difficult. And finally, polyvinyl alcohol is poorly compostible, in other words it is not biodegradable in the strict sense of the word.
The purpose of this invention is to provide a layer material which exhibits improvements to the aforementioned properties and which can be used as airtight and biodegradable packaging materials. To achieve this purpose, the layer material is primarily characterized in what is presented in the characteristic part of the accompanying claim 1.
The invention combines the excellent properties of polyhydroxyalcanoate and polylactide.
By using two separate polyhydroxyalcanoate layers, such as polyhydroxybutyric- based layers, particularly hydroxybutyiic-hydroxyvaleric copolymer layers, good barrier properties can be achieved with layers of great thinness, even of only micrometers thick, when they are combined with polylactic acid, i.e. polylactide (PLA) which improves the processability of the material. Polylactide exhibits good adhesion properties and it does not stick to the surface of the chill roll in coextrusion which means that also the coextrusion chances of the hydroxybutyric/ hydroxyvaleric copolymers are improved, among other things edge weaving is reduced and the nucleant can be omitted.
The use of two separate polyhydroxyalcanoate layers ensures that the microscopic pinholes which may develop to the layers are not formed at the same spot, which improves barrier properties.
Because of the plastic layer structure described, the gas and grease tightness are improved, and better resistance to folding and creasing can be achieved. The invention is described in more detail in the following with reference to the accompanying drawings in which
Figure 1 shows a schematic view of the layer material according to the invention, and
Figure 2 shows the process for manufacturing the material.
Figure 1 includes a cellulose-based and naturally decomposing basic layer 1, which gives the product its strength, the basis weight of which may vary within the known values for paper and cardboard. Laminated on top of the basic layer 1 by coextrusion, are the following layers starting from the basic layer 1: A polylactide layer 1 (PLA) which attaches the other plastic layers to the basic layer by adhesion, a hydroxybutyric/hydroxyvaleric copolymer layer 3 (HB/HV), a polylactide layer 4, a hydroxybutyric/hydroxyvaleric copolymer layer 5 and a polylactide layer 6 which forms the outer layer. As is apparent from the aforesaid, all the plastic layers are biodegradable which in this case denotes that their polymer structures are naturally such that the polymer chains degrade under compost conditions. The layer material can be used as a packaging material for purposes when the escape of water vapour, oxygen or aroma is wished to be prevented, particularly for the packaging of food stuffs, cosmetics and industrial chemicals.
The polylactide layer 4 in the middle also attaches the HB/HV layers 3 and 5, which act as barrier layers, to each other.
The HB/HV layers 3 and 5 can be formed very thin, and their barrier properties as separate layers are better than those of a uniform layer of the same total thickness. Due to the aforesaid properties, the HB/HV qualities may be more freely selected.
The heat-sealing properties of the outermost PLA layer may be utilized in forming food stuff packaging containers or in attaching additional layers to the material. A further good property of polylactide is its inexpensiveness.
By using polylactide (PLA) and HB/HV copolymer together as several separate layers (3 layers of PLA and 2 layer of HB/HV), the good adhesion and surface properties of the first and the good barrier properties of the latter can be utilized efficiently. The plastic layers are usually in contact with the packaged product. It is also possible to further add the same layers to the layer material in Fig. 1 so that they succeed one another by turns as described. On the other hand, the outermost PLA layer 6 can be omitted, in which case the layer 5 forms the outer layer. This is suitable for liquid packaging containers because of the good water resistance of HB/HV or its equivalent. If the outer layer is PLA it is suitable to the packaging of greasy food stuffs.
In layers 3 and 5, other polyhydroxyalcanoate may also be used, preferably polyhydroxybutyrate (PHB) or its copolymer with another hydroxyalcanoate, such as the aforementioned HB/HV.
The hydroxybutyric/hydroxyvaleric copolymer may be, for example, one with 92
% of hydroxybutyric units and 8 % of hydroxyvaleric units, which is sold under the trade name "BIOPOL" by the Zeneca Ltd. The number of hydroxyvaleric units in the copolymer may vary, and it may be within, for example, the range 1 - 20 p-
%.
In principle it would be possible to replace the layers 3 and 5 with only one polyhydroxyalcanoate layer mentioned above, in which case the structure in Fig. 1 would be a three-layer structure.
The basic layer 1 may be paper used in food stuff packaging containers, cardboard or preferably greaseproof paper which has good grease and aroma tightness, for example 100 - 600 s as Linden tightness. The basis weight of the basic layer may vary considerably, for example in the range 30 - 500 g m2.
Figure 2 shows the principle for manufacturing the layer material. The coextruder 7 comprises a feed block 8 into which the aforesaid two biodegradable polymer materials are fed (marked with letters HB/HV and PLA). The feed block arranges the materials into five layers one on top of each other, after which the forming die 9 spreads them into a film of full-width which is lead into the nip between the press roll 10 and the control roll 11 , into which nip the material forming the basic layer 1 is brought from its own roll. The finished layer material is lead along the surface of the control roll 11 to further processing In the drawing, a possibility to add an additional layer on top of the plastic layer comprised of layers 2 - 6 is marked with a dotted line, the additional layer being preferably also a cellulose- based naturally decomposing material. In this case, there could be a thinner paper on one side of the plastic layers and a thicker packaging cardboard on the other side.

Claims

Claims
1. A layer material which comprises a cellulose-based and naturally decomposing basic layer (1) and, on top of this basic layer, layers (3, 5) of polyhydroxyalcanoate, such as hydroxybutyric/hydroxyvaleric copolymer
(HB/HV), characterized in that between the aforesaid layers (3, 5) and between these layers and the basic layer (1) there is a layer (4, 2) of biodegradable polylactide (PLA)
2. A layer material according to claim 1, characterized in that on top of the outermost polyhydroxyalcanoate layer, such as the hydroxybutyric/hydroxyvaleric layer (5), there is also a layer (6) of biodegradable polylactide as the outer layer to the plastic layers.
3. A layer material according to claim 1 or 2, characterized in that the plastic layers (2 - 6) are formed on top of the basic layer (1) by coextrusion.
PCT/FI1997/000184 1996-04-04 1997-03-24 Layer material WO1997037848A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US08/952,902 US6080478A (en) 1996-04-04 1997-03-24 Biodegradable multilayer material
DE1997622560 DE69722560T2 (en) 1996-04-04 1997-03-24 COMPOSITE MATERIALS.
EP97914338A EP0842048B1 (en) 1996-04-04 1997-03-24 Layer material
JP53586797A JPH11506990A (en) 1996-04-04 1997-03-24 Layer material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI961543A FI99268C (en) 1996-04-04 1996-04-04 layer Material
FI961543 1996-04-04

Publications (1)

Publication Number Publication Date
WO1997037848A1 true WO1997037848A1 (en) 1997-10-16

Family

ID=8545797

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI1997/000184 WO1997037848A1 (en) 1996-04-04 1997-03-24 Layer material

Country Status (6)

Country Link
US (1) US6080478A (en)
EP (1) EP0842048B1 (en)
JP (1) JPH11506990A (en)
DE (1) DE69722560T2 (en)
FI (1) FI99268C (en)
WO (1) WO1997037848A1 (en)

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DE69722560T2 (en) 2004-05-06
FI99268C (en) 1998-02-25
US6080478A (en) 2000-06-27
FI961543A0 (en) 1996-04-04
EP0842048B1 (en) 2003-06-04
DE69722560D1 (en) 2003-07-10
FI99268B (en) 1997-11-14
EP0842048A1 (en) 1998-05-20

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